Porous inorganic/organic homogenous copolymeric hybrid materials for chromatographic separation and process for the preparation thereof

ABSTRACT

The present invention relates to porous inorganic/organic homogenous copolymeric hybrid material materials, including particulates and monoliths, methods for their manufacture, and uses thereof, e.g., as chromatographic separations materials.

RELATED APPLICATIONS

This application claims benefit of and is a continuation ofInternational Application No. PCT/US03/34776, filed Oct. 30, 2003 anddesignating the United States, which claims benefit of and priority toU.S. Provisional Application No. 60/422,580, filed Oct. 30, 2002. Theentire contents of these applications are incorporated herein byreference.

BACKGROUND OF THE INVENTION

Packing materials for liquid chromatography (LC) are generallyclassified into two types: organic materials, e.g., polydivinylbenzene,and inorganic materials, e.g., silica.

As stationary phases for HPLC, silica-based materials result in columnsthat do not show evidence of shrinking or swelling and are mechanicallystrong. However, limited hydrolytic stability is a drawback withsilica-based columns, because silica may be readily dissolved underalkaline conditions, generally pH>8.0, leading to the subsequentcollapse of the chromatographic bed. Additionally, the bonded phase on asilica surface may be removed from the surface under acidic conditions,generally pH<2.0, and eluted off the column by the mobile phase, causingloss of analyte retention.

On the other hand, many organic materials are chemically stable againststrongly alkaline and strongly acidic mobile phases, allowingflexibility in the choice of mobile phase pH. However, organicchromatographic materials generally result in columns with lowefficiency, leading to inadequate separation performance, particularlywith low molecular-weight analytes. Furthermore, many organicchromatographic materials shrink and swell when the composition of themobile phase is changed. In addition, most organic chromatographicmaterials do not have the mechanical strength of typical chromatographicsilica.

In order to overcome the above-mentioned deficiencies while maintainingthe beneficial properties of purely organic and purely inorganicmaterials, others have attempted to simply mix organic and inorganicmaterials. For example, others have previously attempted to produce suchmaterials for optical sensors or gas separation membranes that aremixtures of organic polymers (e.g., poly(2-methyl-2-oxazoline),poly(N-vinylpyrrolidone), polystyrene, or poly(N,N-dimethylacrylamide)dispersed within silica. See, e.g., Chujo, Polymeric Materials: Science& Engineering, 84, 783 (2001); Tamaki, Polymer Bull., 39, 303 (1997);and Chujo, MRS Bull., 389 (May 2001). These materials, however, were notuseful for any liquid based separation application because they aretranslucent and non-porous. As a result, these materials lack capacityas a separation material.

Still others have attempted to make materials that have inorganic andorganic components covalently bound to each other. See, e.g., Feng, Q.,J. Mater. Chem. 10, 2490-94 (2000), Feng, Q., Polym. Preprints 41,515-16 (2000), Wei, Y., Adv. Mater. 12, 1448-50 (2000), Wei, Y. J.Polym. Sci. 18, 1-7 (2000). These materials, however, only contain verylow amounts of organic material, i.e., less than 1% C, and as a resultthey function essentially as inorganic silica gels. Furthermore, thesematerials are non-porous until they are ground to irregular particlesand then extracted to remove template porogen molecules. Accordingly, itis not possible to make porous monolithic materials that which have auseful capacity as a separation material. Also, irregularly-shapedparticles are generally more difficult to pack than spherical particles.It is also known that columns packed with irregularly-shaped particlesgenerally exhibit poorer packed bed stability than spherical particlesof the same size. The template agents used in the synthesis of thesematerials are nonsurfactant optically active compounds, and the use ofsuch compounds limits the range of porogen choices and increases theircost. The properties of these materials make them undesirable for use asLC packing materials.

SUMMARY OF THE INVENTION

The present invention provides a solution to the above-mentioneddeficiencies. In particular, the present invention relates to a novelmaterial for chromatographic separations, processes for its preparation,and separations devices containing the chromatographic material. Forexample, the invention pertains to a porous inorganic/organic homogenouscopolymeric hybrid material having at least about 10% carbon content bymass. Also, the invention relates to a porous inorganic/organichomogenous copolymeric hybrid material of spherical particles.Additionally, the invention relates to a porous inorganic/organichomogenous copolymeric hybrid monolith material. The present inventionprovides porous inorganic/organic homogenous copolymeric hybridmaterials of the formula:

(A)_(x)(B)_(y)(C)_(z)

wherein the order of repeat units A, B, and C may be random, block, or acombination of random and block;

A is an organic repeat unit which is covalently bonded to one or morerepeat units A or B via an organic bond;

B is an organosiloxane repeat unit which is bonded to one or more repeatunits B or C via an inorganic siloxane bond and which may be furtherbonded to one or more repeat units A or B via an organic bond;

C is an inorganic repeat unit which is bonded to one or more repeatunits B or C via an inorganic bond; and

x, y are positive numbers and z is a non negative number, wherein

when z=0, then 0.002≦x/y≦210, and when z≠0, then

0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210.

Certain other porous inorganic/organic homogenous copolymeric hybridmaterials provided by the present invention include those materials ofthe formula:

(A)_(x)(B)_(y)(B*)_(y)*(C)_(z)

wherein the order of repeat units A, B, B*, and C may be random, block,or a combination of random and block;

A is an organic repeat unit which is covalently bonded to one or morerepeat units A or B via an organic bond;

B is an organosiloxane repeat unit which is bonded to one or more repeatunits B, B* or C via an inorganic siloxane bond and which may be furtherbonded to one or more repeat units A or B via an organic bond;

B* is an organosiloxane repeat unit that does not have reactive (i.e.,polymerizable) organic components and may further have a protectedfunctional group that may be deprotected after polymerization;

C is an inorganic repeat unit which is bonded to one or more repeatunits B or B* or C via an inorganic bond; and

x, y are positive numbers and z is a non negative number, wherein

when z=0, then 0.002≦x/(y+y*)≦210, and when z≠0, then

0.0003≦(y+y*)/z≦500 and 0.002≦x/(y+y*+z)≦210.

In particular, one aspect of the invention is a porous inorganic/organichomogenous copolymeric hybrid material (either a monolith or particles)of the formula:

(A)_(x)(B)_(y)(C)_(z)  Formula I

wherein the order of repeat units A, B, and C may be random, block, or acombination of random and block; A is an organic repeat unit which iscovalently bonded to one or more repeat units A or B via an organic bond(e.g., a polymerized olefin); B is an organosiloxane repeat unit whichis bonded to one or more repeat units B or C via an inorganic siloxanebond and which may be further bonded to one or more repeat units A or Bvia an organic bond; C is an inorganic repeat unit which is bonded toone or more repeat units B or C via an inorganic bond; and0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210.

One skilled in the art will appreciate that such materials may haveunreacted end groups, e.g., SiOH, Si(OH)₂, or Si(OH)₃, or unpolymerizedolefins.

Additionally, the present invention relates to a novel material forchromatographic separations, processes for its preparation, andseparations devices containing the chromatographic material. Inparticular, one aspect of the invention is a porous inorganic/organichomogenous copolymeric hybrid material of the formula:

(A)_(x)(B)_(y)(B*)_(y)*(C)_(z)  Formula II

wherein the order of repeat units A, B, B*, and C may be random, block,or a combination of random and block; and A, B, B*, C, x, y, and z areas defined above. The relative stoichiometry of the A to (B+B*) to Ccomponents is the same as above, e.g, 0.0003≦(y+y*)/z≦500 and0.002≦x/(y+y*+z)≦210.

Repeat unit A may be derived from a variety of organic monomer reagentspossessing one or more polymerizable moieties, capable of undergoingpolymerization, e.g., a free radical-mediated polymerization. A monomersmay be oligomerized or polymerized by a number of processes andmechanisms including, but not limited to, chain addition and stepcondensation processes, radical, anionic, cationic, ring-opening, grouptransfer, metathesis, and photochemical mechanisms.

Repeat unit B may be derived from several mixed organic-inorganicmonomer reagents possessing two or more different polymerizablemoieties, capable of undergoing polymerization, e.g., a freeradical-mediated (organic) and hydrolytic (inorganic) polymerization. Bmonomers may be oligomerized or polymerized by a number of processes andmechanisms including, but not limited to, chain addition and stepcondensation processes, radical, anionic, cationic, ring-opening, grouptransfer, metathesis, and photochemical mechanisms.

Repeat unit C may be —SiO₂— and may be derived from an alkoxysilane,such as tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS).

Another aspect of the invention is a porous inorganic/organic homogenouscopolymeric hybrid material of the formula:

(A)_(x)(B)_(y)  Formula III

wherein the order of repeat units A and B may be random, block, or acombination of random and block; A is an organic repeat unit which iscovalently bonded to one or more repeat units A or B via an organic bond(e.g., a polymerized olefin); B is an organosiloxane repeat unit whichmay or may not be bonded to one or more repeat units B via an inorganicsiloxane bond and which may be further bonded to one or more repeatunits A or B via an organic bond; and 0.002≦x/y≦210.

Repeat unit A may be derived from a variety of organic monomer reagentspossessing one or more polymerizable moieties, capable of undergoingpolymerization, e.g., a free radical-mediated polymerization. A monomersmay be oligomerized or polymerized by a number of processes andmechanisms including, but not limited to, chain addition and stepcondensation processes, radical, anionic, cationic, ring-opening, grouptransfer, metathesis, and photochemical mechanisms.

Repeat unit B may be derived from several mixed organic-inorganicmonomer reagents possessing two or more different polymerizablemoieties, capable of undergoing polymerization, e.g., a freeradical-mediated (organic) and hydrolytic (inorganic) polymerization. Bmonomers may be oligomerized or polymerized by a number of processes andmechanisms including, but not limited to, chain addition and stepcondensation processes, radical, anionic, cationic, ring-opening, grouptransfer, metathesis, and photochemical mechanisms.

One skilled in the art will appreciate that such materials may haveunreacted end groups, e.g., SiOR, Si(OR)₂, or Si(OR)₃, where R═H orC₁-C₅ alkane, or unpolymerized olefins.

Another aspect of the invention is a porous inorganic/organic homogenouscopolymeric hybrid material of the formula:

(A)_(x)(B)_(y)(B*)_(y)*  Formula IV

wherein the order of repeat units A, B, and B* may be random, block, ora combination of random and block; A is an organic repeat unit which iscovalently bonded to one or more repeat units A or B via an organic bond(e.g., a polymerized olefin); B is an organosiloxane repeat unit whichmay or may not be bonded to one or more repeat units B or B* via aninorganic siloxane bond and which may be further bonded to one or morerepeat units A or B via an organic bond; B* is an organosiloxane repeatunit that does not have reactive (i.e., polymerizable) organiccomponents and may further have a protected functional group that may bedeprotected after polymerization. The relative stoichiometry of the A to(B+B*) components is the same as above, e.g., 0.002≦x/(y+y*)≦210.

Repeat unit A may be derived from a variety of organic monomer reagentspossessing one or more polymerizable moieties, capable of undergoingpolymerization, e.g., a free radical-mediated polymerization. A monomersmay be oligomerized or polymerized by a number of processes andmechanisms including, but not limited to, chain addition and stepcondensation processes, radical, anionic, cationic, ring-opening, grouptransfer, metathesis, and photochemical mechanisms.

Repeat unit B may be derived from several mixed organic-inorganicmonomer reagents possessing two or more different polymerizablemoieties, capable of undergoing polymerization, e.g., a freeradical-mediated (organic) and hydrolytic (inorganic) polymerization. Bmonomers may be oligomerized or polymerized by a number of processes andmechanisms including, but not limited to, chain addition and stepcondensation processes, radical, anionic, cationic, ring-opening, grouptransfer, metathesis, and photochemical mechanisms.

One skilled in the art will appreciate that such materials may haveunreacted end groups, e.g., SiOR, Si(OR)₂, or Si(OR)₃, where R═H orC₁-C₅ alkane, or unpolymerized olefins.

By way of example, the present invention pertains to a porousinorganic/organic homogenous copolymeric hybrid material of the formula:

where R₁ is H, F, Cl, Br, I, lower alkyl (e.g., CH₃ or CH₂CH₃); R₂ andR₃ are each independently H, F, Cl, Br, I, alkane, substituted alkane,alkene, substituted alkene, aryl, substituted aryl, cyano, ether,substituted ether, embedded polar group; R₄ and R₅ are eachindependently H, F, Cl, Br, I, alkane, substituted alkane, alkene,substituted alkene, aryl, substituted aryl, ether, substituted ether,cyano, amino, substituted amino, diol, nitro, sulfonic acid, cation oranion exchange groups, 0≦a≦2x, 0≦b≦4, and 0≦c≦4, provided that b+c≦4when a=1; 1≦d≦20, and 0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210.

The invention also relates to porous inorganic/organic homogenouscopolymeric hybrid materials prepared, e.g., by the steps ofcopolymerizing an organic olefin monomer with an alkenyl-functionalizedorganosiloxane, and hydrolytic condensation of the product of the otherstep with a tetraalkoxysilane. The copolymerizing and condensation stepsmay be performed substantially simultaneously or sequentially.

The material of the invention may be used as a liquid chromatographystationary phase; a sequestering reagent; a solid support forcombinatorial chemistry; a solid support for oligosaccharide,polypeptide, or oligonucleotide synthesis; a solid support for abiological assay; a capillary biological assay device for massspectrometry; a template for a controlled large pore polymer film; acapillary chromatography stationary phase; an electrokinetic pumppacking material; a polymer additive; a catalyst; or a packing materialfor a microchip separation device.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of the mechanical strength results for two porousinorganic/organic homogenous copolymeric hybrid materials of theinvention (Examples 3b and 3v; 3 μm fractions), commercially availablesilica based (5 μm Symmetry® C₁₈, Waters Corporation) and polymericbased (7 μm Ultrastyragel™ 10⁶ Å and 7 μm Ultrastyragel™ 10⁴ Å, WatersCorporation) materials wherein the figure legend is A=Symmetry® C₁₈, B=3μm Example 3b, C=3 μm Example 3v, D=7 μm Ultrastyragel™ 10⁶ Å, E=7 μmUltrastyragel™ 10⁴ Å.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be more fully illustrated by reference to thedefinitions set forth below.

The term “monolith” is intended to include a porous, three-dimensionalmaterial having a continuous interconnected pore structure in a singlepiece. A monolith is prepared, for example, by casting precursors into amold of a desired shape. The term monolith is meant to be distinguishedfrom a collection of individual particles packed into a bed formation,in which the end product comprises individual particles. Such monolithmaterials are described in detail in international patent applicationnumber PCT/US02/25193 (attorney docket number WCZ-025CPPC), filed Aug.8, 2002, and U.S. provisional patent application No. 60/311,445(attorney docket number WCZ-025- 1), filed Aug. 9, 2001, both of whichare incorporated herein by reference.

The terms “coalescing” and “coalesced” are intended to describe amaterial in which several individual components have become coherent toresult in one new component by an appropriate chemical or physicalprocess, e.g., heating. The term coalesced is meant to be distinguishedfrom a collection of individual particles in close physical proximity,e.g., in a bed formation, in which the end product comprises individualparticles.

As used herein, the term “porous inorganic/organic homogenouscopolymeric hybrid material” or “porous inorganic/organic homogenouscopolymeric hybrid monolith material” includes materials comprisinginorganic repeat units (e.g., comprising O—Si—O bonds between repeatunits), organic repeat units (e.g., comprising C—C bonds between repeatunits), and mixed organic-inorganic repeat units (e.g., comprising bothC—C and O—Si—O bonds between repeat units). The term “porous” indicatesthat the microscopic structure of the material contains pores of ameasurable volume, so that the materials can be used, for example, assolid supports in chromatography. The term “inorganic/organiccopolymeric hybrid” indicates that the material comprises a copolymer oforganic, inorganic, and mixed organic/inorganic repeat units. The term“homogenous” indicates that the structure of the material at thechemical level is substantially interconnected via chemical bonds, asopposed to the prior art materials that simply comprise mixtures ofdiscrete organic and inorganic materials. The term “hybrid” refers to amaterial having chemical bonds among inorganic and organic repeat unitsof a composite material thereby forming a matrix throughout the materialitself, as opposed to a mixture of discrete chemical compounds.

Polyorganoalkoxysiloxane (POS) and polyalkylalkoxysiloxane (PAS) arelarge molecules, either linear or preferably three-dimensional networks,that are formed by the condensation of silanols, where the silanols areformed, e.g., by hydrolysis of halo- or alkoxy-substituted silanes.

As used herein, the term “protecting group” means a protected functionalgroup which may be intended to include chemical moieties that shield afunctional group from chemical reaction or interaction such that uponlater removal (“deprotection”) of the protecting group, the functionalgroup can be revealed and subjected to further chemistry. For example, amonomer used in the synthesis of the materials of the present inventionmay contain The term also includes a functional group which that doesnot interfere with the various polymerization and condensation reactionsused in the synthesis of the materials of the invention, but which thatmay be converted after synthesis of the material into a functional groupwhich that may itself be further derivatized. For example, an organicmonomer reagent A may contain an aromatic nitro group which that wouldnot interfere with the polymerization or condensation reactions.However, after these polymerization and condensation reactions have beencarried out, the nitro group may be reduced to an amino group (e.g., ananiline), which itself may then be subjected to further derivatizationby a variety of means known in the art. In this manner, additionalfunctional groups may be incorporated into the material after thesyntheses of the material itself. See generally, Greene, T. W. and Wuts,P. G. M. “Protective Groups in Organic Synthesis,” Second Edition,Wiley, 1991. In some cases, preferable protecting groups strategies donot involve the use of heavy metals (e.g., transition metals) in theprotection or deprotection step as these metals may be difficult toremove from the material completely.

The porous inorganic/organic homogenous copolymeric hybrid particles andmonolith materials possess both organic groups and silanol groups whichmay additionally be substituted or derivatized with a surface modifier.“Surface modifiers” include (typically) organic groups which impart acertain chromatographic functionality to a chromatographic stationaryphase. Surface modifiers such as disclosed herein are attached to thebase material, e.g., via derivatization or coating and latercrosslinking, imparting the chemical character of the surface modifierto the base material. In one embodiment, the organic groups of thehybrid materials react to form an organic covalent bond with a surfacemodifier. The modifiers may form an organic covalent bond to thematerial's organic group via a number of mechanisms well known inorganic and polymer chemistry including, but not limited to,nucleophilic, electrophilic, cycloaddition, free-radical, carbene,nitrene, and carbocation reactions. Organic covalent bonds are definedto involve the formation of a covalent bond between the common elementsof organic chemistry including, but not limited to, hydrogen, boron,carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, and the halogens.In addition, carbon-silicon and carbon-oxygen-silicon bonds are definedas organic covalent bonds, whereas silicon-oxygen-silicon bonds that arenot defined as organic covalent bonds. In general, the porousinorganic/organic homogenous copolymeric hybrid particles and monolithmaterials may be modified by an organic group surface modifier, asilanol group surface modifier, a polymeric coating surface modifier,and combinations of the aforementioned surface modifiers.

For example, silanol groups are surface modified with compounds havingthe formula Z_(a)(R′)_(b)Si—R, where Z═Cl, Br, I, C₁-C₅ alkoxy,dialkylamino, e.g., dimethylamino, or trifluoromethanesulfonate; a and bare each an integer from 0 to 3 provided that a+b=3; R′ is a C₁-C₆straight, cyclic or branched alkyl group, and R is a functionalizinggroup. R′ may be, e.g., methyl, ethyl, propyl, isopropyl, butyl,t-butyl, sec-butyl, pentyl, isopentyl, hexyl or cyclohexyl; preferably,R′ is methyl. In certain embodiments, the organic groups may besimilarly functionalized.

The functionalizing group R may include alkyl, aryl, cyano, amino, diol,nitro, cation or anion exchange groups, or embedded polarfunctionalities. Examples of suitable R functionalizing groups includeC₁-C₃₀ alkyl, including C₁-C₂₀, such as octyl (C₈), octadecyl (C₁₈), andtriacontyl (C₃₀); alkaryl, e.g., C₁-C₄-phenyl; cyanoalkyl groups, e.g.,cyanopropyl; diol groups, e.g., propyldiol; amino groups, e.g.,aminopropyl; and alkyl or aryl groups with embedded polarfunctionalities, e.g., carbamate functionalities such as disclosed inU.S. Pat. No. 5,374,755, the text of which is incorporated herein byreference. Such groups include those of the general formula

wherein l, m, o, r, and s are 0 or 1, n is 0, 1, 2 or 3 p is 0, 1, 2, 3or 4 and q is an integer from 0 to 19; R₃ is selected from the groupconsisting of hydrogen, alkyl, cyano and phenyl; and Z, R′, a and b aredefined as above. Preferably, the carbamate functionality has thegeneral structure indicated below:

wherein R⁵ may be, e.g., cyanoalkyl, t-butyl, butyl, octyl, dodecyl,tetradecyl, octadecyl, or benzyl. Advantageously, R⁵ is octyl, dodecyl,or octadecyl.

In a preferred embodiment, the surface modifier may be anorganotrihalosilane, such as octyltrichlorosilane oroctadecyltrichlorosilane. In an additional preferred embodiment, thesurface modifier may be a halopolyorganosilane, such asoctyldimethylchlorosilane or octadecyldimethylchlorosilane. In certainembodiments the surface modifier is octadecyltrimethoxysilane oroctadecyltrichlorosilane.

In another embodiment, the hybrid material's organic groups and silanolgroups are both surface modified or derivatized. In another embodiment,the hybrid materials are surface modified by coating with a polymer.

The term “aliphatic group” includes organic compounds characterized bystraight or branched chains, typically having between 1 and 22 carbonatoms. Aliphatic groups include alkyl groups, alkenyl groups and alkynylgroups. In complex structures, the chains may be branched orcross-linked. Alkyl groups include saturated hydrocarbons having one ormore carbon atoms, including straight-chain alkyl groups andbranched-chain alkyl groups. Such hydrocarbon moieties may besubstituted on one or more carbons with, for example, a halogen, ahydroxyl, a thiol, an amino, an alkoxy, an alkylcarboxy, an alkylthio,or a nitro group. Unless the number of carbons is otherwise specified,“lower aliphatic” as used herein means an aliphatic group, as definedabove (e.g., lower alkyl, lower alkenyl, lower alkynyl), but having fromone to six carbon atoms. Representative of such lower aliphatic groups,e.g., lower alkyl groups, are methyl, ethyl, n-propyl, isopropyl,2-chloropropyl, n-butyl, sec-butyl, 2-aminobutyl, isobutyl, tert-butyl,3-thiopentyl, and the like. As used herein, the term “nitro” means —NO₂;the term “halogen” designates —F, —Cl, —Br or —I; the term “thiol” meansSH; and the term “hydroxyl” means —OH. Thus, the term “alkylamino” asused herein means an alkyl group, as defined above, having an aminogroup attached thereto. Suitable alkylamino groups include groups having1 to about 12 carbon atoms, preferably from 1 to about 6 carbon atoms.The term “alkylthio” refers to an alkyl group, as defined above, havinga sulfhydryl group attached thereto. Suitable alkylthio groups includegroups having 1 to about 12 carbon atoms, preferably from 1 to about 6carbon atoms. The term “alkylcarboxyl” as used herein means an alkylgroup, as defined above, having a carboxyl group attached thereto. Theterm “alkoxy” as used herein means an alkyl group, as defined above,having an oxygen atom attached thereto. Representative alkoxy groupsinclude groups having 1 to about 12 carbon atoms, preferably 1 to about6 carbon atoms, e.g., methoxy, ethoxy, propoxy, tert-butoxy and thelike. The terms “alkenyl” and “alkynyl” refer to unsaturated aliphaticgroups analogous to alkyls, but which contain at least one double ortriple bond respectively. Suitable alkenyl and alkynyl groups includegroups having 2 to about 12 carbon atoms, preferably from 1 to about 6carbon atoms.

The term “alicyclic group” includes closed ring structures of three ormore carbon atoms. Alicyclic groups include cycloparaffins or naphtheneswhich are saturated cyclic hydrocarbons, cycloolefins which areunsaturated with two or more double bonds, and cycloacetylenes whichhave a triple bond. They do not include aromatic groups. Examples ofcycloparaffins include cyclopropane, cyclohexane, and cyclopentane.Examples of cycloolefins include cyclopentadiene and cyclooctatetraene.Alicyclic groups also include fused ring structures and substitutedalicyclic groups such as alkyl substituted alicyclic groups. In theinstance of the alicyclics such substituents may further comprise alower alkyl, a lower alkenyl, a lower alkoxy, a lower alkylthio, a loweralkylamino, a lower alkylcarboxyl, a nitro, a hydroxyl, —CF₃, —CN, orthe like.

The term “heterocyclic group” includes closed ring structures in whichone or more of the atoms in the ring is an element other than carbon,for example, nitrogen, sulfur, or oxygen. Heterocyclic groups may besaturated or unsaturated and heterocyclic groups such as pyrrole andfuran may have aromatic character. They include fused ring structuressuch as quinoline and isoquinoline. Other examples of heterocyclicgroups include pyridine and purine. Heterocyclic groups may also besubstituted at one or more constituent atoms with, for example, ahalogen, a lower alkyl, a lower alkenyl, a lower alkoxy, a loweralkylthio, a lower alkylamino, a lower alkylcarboxyl, a nitro, ahydroxyl, —CF₃, —CN, or the like. Suitable heteroaromatic andheteroalicyclic groups generally will have 1 to 3 separate or fusedrings with 3 to about 8 members per ring and one or more N, O or Satoms, e.g., coumarinyl, quinolinyl, pyridyl, pyrazinyl, pyrimidyl,furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl,benzofuranyl, benzothiazolyl, tetrahydrofuranyl, tetrahydropyranyl,piperidinyl, morpholino and pyrrolidinyl.

The term “aromatic group” includes unsaturated cyclic hydrocarbonscontaining one or more rings. Aromatic groups include 5- and 6-memberedsingle-ring groups which may include from zero to four heteroatoms, forexample, benzene, pyrrole, furan, thiophene, imidazole, oxazole,thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine andpyrimidine, and the like. The aromatic ring may be substituted at one ormore ring positions with, for example, a halogen, a lower alkyl, a loweralkenyl, a lower alkoxy, a lower alkylthio, a lower alkylamino, a loweralkylcarboxyl, a nitro, a hydroxyl, —CF₃, —CN, or the like.

The term “alkyl” includes saturated aliphatic groups, includingstraight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl(alicyclic) groups, alkyl substituted cycloalkyl groups, and cycloalkylsubstituted alkyl groups. In certain embodiments, a straight chain orbranched chain alkyl has 30 or fewer carbon atoms in its backbone, e.g.,C₁-C₃₀ for straight chain or C₃-C₃₀ for branched chain. In certainembodiments, a straight chain or branched chain alkyl has 20 or fewercarbon atoms in its backbone, e.g., C₁-C₂₀ for straight chain or C₃-C₂₀for branched chain, and more preferably 18 or fewer. Likewise, preferredcycloalkyls have from 4-10 carbon atoms in their ring structure, andmore preferably have 4-7 carbon atoms in the ring structure. The term“lower alkyl” refers to alkyl groups having from 1 to 6 carbons in thechain, and to cycloalkyls having from 3 to 6 carbons in the ringstructure.

Moreover, the term “alkyl” (including “lower alkyl”) as used throughoutthe specification and claims includes both “unsubstituted alkyls” and“substituted alkyls,” the latter of which refers to alkyl moietieshaving substituents replacing a hydrogen on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy,aryloxycarbonyloxy, carboxylate, alkylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato,phosphinato, cyano, amino (including alkyl amino, dialkylamino,arylamino, diarylamino, and alkylarylamino), acylamino (includingalkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino,imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate,sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido,heterocyclyl, aralkyl, or an aromatic or heteroaromatic moiety. It willbe understood by those skilled in the art that the moieties substitutedon the hydrocarbon chain may themselves be substituted, if appropriate.Cycloalkyls may be further substituted, e.g., with the substituentsdescribed above. An “aralkyl” moiety is an alkyl substituted with anaryl, e.g., having 1 to 3 separate or fused rings and from 6 to about 18carbon ring atoms, e.g., phenylmethyl (benzyl).

The term “aryl” includes 5- and 6-membered single-ring aromatic groupsthat may include from zero to four heteroatoms, for example,unsubstituted or substituted benzene, pyrrole, furan, thiophene,imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine,pyridazine and pyrimidine, and the like. Aryl groups also includepolycyclic fused aromatic groups such as naphthyl, quinolyl, indolyl,and the like. The aromatic ring may be substituted at one or more ringpositions with such substituents, e.g., as described above for alkylgroups. Suitable aryl groups include unsubstituted and substitutedphenyl groups. The term “aryloxy” as used herein means an aryl group, asdefined above, having an oxygen atom attached thereto. The term“aralkoxy” as used herein means an aralkyl group, as defined above,having an oxygen atom attached thereto. Suitable aralkoxy groups have 1to 3 separate or fused rings and from 6 to about 18 carbon ring atoms,e.g., O-benzyl.

The term “amino,” as used herein, refers to an unsubstituted orsubstituted moiety of the formula —NR_(a)R_(b), in which R_(a) and R_(b)are each independently hydrogen, alkyl, aryl, or heterocyclyl, or R_(a)and R_(b), taken together with the nitrogen atom to which they areattached, form a cyclic moiety having from 3 to 8 atoms in the ring.Thus, the term “amino” includes cyclic amino moieties such aspiperidinyl or pyrrolidinyl groups, unless otherwise stated. An“amino-substituted amino group” refers to an amino group in which atleast one of R_(a) and R_(b), is further substituted with an aminogroup.

Porous inorganic/organic homogenous copolymeric hybrid material of theinvention may be made as described below and in the specific instancesillustrated in the Examples. Porous spherical particles of hybrid silicamay, in one embodiment, be prepared by the steps of (a) hydrolyticallycondensing an alkenyl-functionalized organosilane with atetraalkoxysilane, (b) copolymerizing the product of step (a) with anorganic olefin monomer, and (c) further hydrolytically condensing theproduct of step (b) to thereby prepare a porous inorganic/organichomogenous copolymeric hybrid material. In this embodiment, steps (b)and (c) may be performed substantially simultaneously. Steps (a) and (b)may be performed in the same reaction vessel.

Alternatively, the materials of the invention may be prepared by thesteps of (a) copolymerizing an organic olefin monomer with analkenyl-functionalized organosilane, and (b) hydrolytically condensingthe product of step (a) with a tetraalkoxysilane in the presence of anon-optically active porogen to thereby prepare a porousinorganic/organic homogenous copolymeric hybrid material. Steps (a) and(b) may be performed in the same reaction vessel.

Also, the materials may be prepared by the steps of substantiallysimultaneously copolymerizing an organic monomer with analkenyl-functionalized organosilane and hydrolytically condensing saidalkenyl-functionalized organosilane with a tetraalkoxysilane to therebyprepare a porous inorganic/organic homogenous copolymeric hybridmaterial.

The copolymerizing step of the foregoing methods may be freeradical-initiated and the hydrolytically condensing step of theforegoing methods may by acid- or base-catalyzed. In the case of acidcatalysis, the acid may be, e.g., hydrochloric acid, hydrobromic acid,hydrofluoric acid, hydroiodic acid, sulfuric acid, formic acid, aceticacid, trichloroacetic acid, trifluoroacetic acid, or phosphoric acid.Likewise, in the case of base catalysis, the base may be ammoniumhydroxide, hydroxide salts of the group I and group II metals, carbonateand hydrogencarbonate salts of the group I metals, or alkoxide salts ofthe group I and group II metals. In the case of free radical-mediatedpolymerizations, a free radical polymerization initiator may be added.Suitable examples of free radical polymerization initiator include2,2′-azobis-[2-(imidazolin-2-yl)propane] dihydrochloride,2,2′-azobisisobutyronitrile, 4,4′-azobis(4-cyanovaleric acid),1,1′-azobis(cyclohexanecarbonitrile), 2,2′-azobis(2-propionamidine)dihydrochloride, 2,2′azobis(2,4-dimethylpentanenitrile),2,2′-azobis(2-methylbutanenitrile), benzoyl peroxide,2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane,2,5-bis(tert-butylperoxy)butane,-2,5-dimethylhexane,2,5-bis(tert-butylperoxy)-2,5-dimethyl-hexyne,bis(1-(tert-butylperoxy)-1-methyethyl)benzene,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butylhydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy isopropyl carbonate, cumene peroxide,cyclohexanone hydroperoxide, dicumyl peroxide, lauroyl peroxide,2,4-pentanedione peroxide, peracetic acid, and potassium persulfate.Additionally, the reaction may be heated following the addition of thefree radical polymerization initiator.

The solvent used in the synthesis of the materials of the invention maybe, e.g, water, methanol, ethanol, propanol, isopropanol, butanol,tert-butanol, pentanol, hexanol, cyclohexanol, hexafluoroisopropanol,cyclohexane, petroleum ethers, diethyl ether, dialkyl ethers,tetrahydrofuran, acetonitrile, ethyl acetate, pentane, hexane, heptane,benzene, toluene, xylene, N,N-dimethylformamide, dimethyl sulfoxide,1-methyl-2-pyrrolidinone, methylene chloride, chloroform, andcombinations thereof, although those skilled in the art will readilyappreciate that others may be used.

In the synthesis of the materials of the invention, a porogen may beused. Examples of suitable porogens include cyclohexanol, toluene,2-ethylhexanoic acid, dibutylphthalate, 1-methyl-2-pyrrolidinone,1-dodecanol, and Triton X-45.

Some examples of organic olefin monomers of the invention includedivinylbenzene, styrene, ethylene glycol dimethacrylate,1-vinyl-2-pyrrolidinone and tert-butylmethacrylate, acrylamide,methacrylamide, N,N′-(1,2-dihydroxyethylene)bisacrylamide,N,N′-ethylenebisacrylamide, N,N′-methylenebisacrylamide, butyl acrylate,ethyl acrylate, methyl acrylate, 2-(acryloxy)-2-hydroxypropylmethacrylate , 3-(acryloxy)-2-hydroxypropyl methacrylate,trimethylolpropane triacrylate, trimethylolpropane ethoxylatetriacrylate, tris[(2-acryloyloxy)ethyl] isocyanurate, acrylonitrile,methacrylonitrile, itaconic acid, methacrylic acid,trimethylsilylmethacrylate, N-[tris(hydroxymethyl)methyl]acrylamide(THMMA) (3-acrylamidopropyl)trimethylammonium chloride (APTA),[3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxideinner salt (MAPDAHI),

Some examples of alkenyl-functionalized organosiloxane monomers includemethacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane,vinyltriethoxysilane, vinyltrimethoxysilane,N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,(3-acryloxypropyl)trimethoxysilane,O-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane,N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane,methacryloxypropylmethyldiethoxysilane,methacryloxypropylmethyldimethoxysilane,methacryloxypropyltris(methoxyethoxy)silane,3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilanehydrochloride,

wherein each R is independently H or a C1-C10 alkyl group (preferablyhydrogen, methyl, ethyl, or propyl) and wherein R′ is independently H ora C1-C10 alkyl group (preferably hydrogen or methyl, ethyl, or propyl).Also, the R groups may be identical and selected from the groupconsisting of hydrogen, methyl, ethyl, or propyl.

Some examples of tetraalkoxysilanes include tetramethoxysilane,tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane.

The methods of the invention may also comprise adding a surfactant orstabilizer. Suitable examples of surfactants include Triton X-45, sodiumdodecylsulfate, tris(hydroxymethyl)aminomethane, and any combinationthereof. Still other examples of surfactants include Triton X100, TritonX305, TLS, Pluronic F-87, Pluronic P-105, Pluronic P-123, sodiumdodecylsulfate (SDS), and Triton X-405. Examples of stabilizers includemethocel and poly(vinyl alcohol).

The method of the invention may also include a step of endcapping freesilanol groups according to methods which are readily known in the art.

The methods of the invention may also include a step of chemicallymodifying the organic olefin or alkenyl-functionalized organisiloxaneprior to copolymerization.

Additionally, the methods of the invention may also include a step ofmodifying surfaces of the hybrid particles by formation of an organiccovalent bond between an organic group of the particle and a surfacemodifier. In this regard, the method may include a further step of byadding a surface modifier selected from the group consisting of anorganic group surface modifier, a silanol group surface modifier, apolymeric coating surface modifier, and combinations thereof, such asZ_(a)(R′)_(b)Si—R, as described herein above. Likewise, the surfacemodifier may be a polymer coating, such as Sylgard®. Other examples ofreagents include octyltrichlorosilane, octadecyltrichlorosilane,octyldimethylchlorosilane, and octadecyldimethylchlorosilane.

In one embodiment of the invention, the surface organic groups of thehybrid silica are derivatized or modified in a subsequent step viaformation of an organic covalent bond between the particle's organicgroup and the modifying reagent. Alternatively, the surface silanolgroups of the hybrid silica are derivatized into siloxane organicgroups, such as by reacting with an organotrihalosilane, e.g.,octadecyltrichlorosilane, or a halopolyorganosilane, e.g.,octadecyldimethylchlorosilane. Alternatively, the surface organic andsilanol groups of the hybrid silica are both derivatized. The surface ofthe thus-prepared material is then covered by the organic groups, e.g.,alkyl, embedded during the gelation and the organic groups added duringthe derivatization process or processes.

In one embodiment, the pore structure of the as-prepared hybrid materialis modified by hydrothermal treatment, which enlarges the openings ofthe pores as well as the pore diameters, as confirmed by nitrogen (N₂)sorption analysis. The hydrothermal treatment is performed by preparinga slurry containing the as-prepared hybrid material and a solution oforganic base in water, heating the slurry in an autoclave at an elevatedtemperature, e.g., about 143 to 168° C., for a period of about 6 to 28h. The pH of the slurry can be adjusted to be in the range of about 8.0to 12.7 using tetraethylammonium hydroxide (TEAH) or TRIS andconcentrated acetic acid. The concentration of the slurry is in therange of about 1 g hybrid material per 5 to 10 mL of the base solution.The thus-treated hybrid material is filtered, and washed with wateruntil the pH of the filtrate reaches about 7, washed with acetone ormethanol, then dried at about 100° C. under reduced pressure for about16 h. The resultant hybrid materials show average pore diameters in therange of about 100-300 Å. The surface of the hydrothermally treatedhybrid material may be modified in a similar fashion to that of thehybrid material that is not modified by hydrothermal treatment asdescribed in the present invention.

Moreover, the surface of the hydrothermally treated hybrid silicacontains organic groups, which can be derivatized by reacting with areagent that is reactive towards the hybrid materials' organic group.For example, vinyl groups on the material can be reacted with a varietyof olefin reactive reagents such as bromine (Br₂), hydrogen (H₂), freeradicals, propagating polymer radical centers, dienes, and the like. Inanother example, hydroxyl groups on the material can be reacted with avariety of alcohol reactive reagents such as isocyanates, carboxylicacids, carboxylic acid chlorides, and reactive organosilanes asdescribed below. Reactions of this type are well known in theliterature, see, e.g., March, J. “Advanced Organic Chemistry,” 3^(rd)Edition, Wiley, New York, 1985; Odian, G. “The Principles ofPolymerization,” 2^(nd) Edition, Wiley, New York, 1981; the texts ofwhich are incorporated herein by reference.

In addition, the surface of the hydrothermally treated hybrid silicaalso contains silanol groups, which can be derivatized by reacting witha reactive organosilane. The surface derivatization of the hybrid silicais conducted according to standard methods, for example by reaction withoctadecyltrichlorosilane or octadecyldimethylchlorosilane in an organicsolvent under reflux conditions. An organic solvent such as toluene istypically used for this reaction. An organic base such as pyridine orimidazole is added to the reaction mixture to catalyze the reaction. Theproduct of this reaction is then washed with water, toluene and acetoneand dried at about 80° C. to 100° C. under reduced pressure for about 16h. The resultant hybrid silica can be further reacted with a short-chainsilane such as trimethylchlorosilane to endcap the remaining silanolgroups, by using a similar procedure described above.

More generally, the surface of the hybrid silica materials may besurface modified with a surface modifier, e.g., Z_(a)(R′)_(b)Si—R, asdescribed herein above.

The functionalizing group R may include alkyl, alkenyl, alkynyl, aryl,cyano, amino, diol, nitro, cation or anion exchange groups, or alkyl oraryl groups with embedded polar functionalities. Examples of suitable Rfunctionalizing groups include C₁-C₃₀ alkyl, including C₁-C₂₀, such asoctyl (C₈), octadecyl (C₁₈), and triacontyl (C₃₀); alkaryl, e.g.,C₁-C₄-phenyl; cyanoalkyl groups, e.g., cyanopropyl; diol groups, e.g.,propyldiol; amino groups, e.g., aminopropyl; and alkyl or aryl groupswith embedded polar functionalities, e.g., carbamate functionalitiessuch as disclosed in U.S. Pat. No. 5,374,755, the text of which isincorporated herein by reference, and as detailed hereinabove. In apreferred embodiment, the surface modifier may be anorganotrihalosilane, such as octyltrichlorosilane oroctadecyltrichlorosilane. In an additional preferred embodiment, thesurface modifier may be a halopolyorganosilane, such asoctyldimethylchlorosilane or octadecyldimethylchlorosilane.Advantageously, R is octyl or octadecyl.

The surface of the hybrid silica materials may also be surface modifiedby coating with a polymer. Polymer coatings are known in the literatureand may be provided generally by polymerization or polycondensation ofphysisorbed monomers onto the surface without chemical bonding of thepolymer layer to the support (type I), polymerization orpolycondensation of physisorbed monomers onto the surface with chemicalbonding of the polymer layer to the support (type II), immobilization ofphysisorbed prepolymers to the support (type III), and chemisorption ofpresynthesized polymers onto the surface of the support (type IV). See,e.g., Hanson et al., J. Chromat. A656 (1993) 369-380, the text of whichis incorporated herein by reference. As noted above, coating the hybridmaterial with a polymer may be used in conjunction with various surfacemodifications described in the invention. In a preferred embodiment,Sylgard® (Dow Coming, Midland, Mich., USA) is used as the polymer.

The term “porogen” refers to a pore forming material, that is a chemicalmaterial dispersed in a material as it is formed that is subsequentlyremoved to yield pores or voids in the material.

The term “end capping” a chemical reaction step in which a resin thathas already been synthesized, but that may have residual unreactedgroups (e.g., silanol groups in the case of a silicon-based inorganicresin) are passivated by reaction with a suitable reagent. For example,again in the case of silicon-based inorganic resins, such silanol groupsmay be methylated with a methylating reagent such ashexamethyldisilazane.

A stabilizer describes reagents which inhibit the coalescence ofdroplets of organic monomer and POS or PAS polymers in an aqueouscontinuous phase. These can include but are not limited to finelydivided insoluble organic or inorganic materials, electrolytes, andwater-soluble polymers. Typical stabilizers are methyl celluloses,gelatins, polyvinyl alcohols, salts of poly(methacrylic acid), andsurfactants. Surfactants (also referred to as emulsifiers or soaps) aremolecules which have segments of opposite polarity and solubilizingtendency, e.g., both hydrophilic and hydrophobic segments.

The instant invention relates to a porous inorganic/organic homogenouscopolymeric hybrid material having at least about 10% carbon content bymass. In preferred embodiments, the materials of the invention areporous inorganic/organic homogenous copolymeric hybrid particles,particularly spherical particles. The carbon content of the material maybe from about 15% to about 90% carbon content by mass, from about 25% toabout 75% carbon content by mass, from about 30% to about 45% carboncontent by mass, from about 31% to about 40% carbon content by mass,from about 32% to about 40% carbon content by mass, or from about 33% toabout 40% carbon content by mass.

In embodiments where the materials of the invention are in the form ofparticles, they have an average diameter of about 0.1 μm to about 30 to60 μm, or about 2.0 μm to about 15 μm. The particulate materials of theinvention also have a large specific surface area, e.g., about 50-800m²/g or 400-700 m²/g.

The materials of the invention also have defined pore volumes that maybe engineered by choosing an appropriate porogen during synthesis (videsupra). By way of example, the materials of the invention may havespecific pore volumes of about 0.25 to 2.5 cm³/g, about 0.4 to 2.0cm³/g, or 0.5 to 1.3 cm³/g. Likewise, the pore diameters of the materialof the invention may be controlled during synthesis (vide supra). Forexample, the materials of the invention may have an average porediameter of about 20 to 300 Å, about 50 to 200 Å, or about 75 to 125 Å.

Because of their hybrid nature, the materials of the invention arestable over a broad pH range. Typically, the material may behydrolytically stable at a pH of about 1 to about 13, about 4 to about11, about 4 to about 10, about 5 to about 9, or about 6 to about 8.

An advantageous feature of the materials of the invention is theirreduced swelling upon solvation with organic solvents than conventionalorganic LC resins. Therefore, in one embodiment, the material swells byless than about 25% (or 15% or 10% or even 5%) by volume upon solvationwith an organic solvent, such as acetonitrile, methanol, ethers (such asdiethyl ether), tetrahydrofuran, dichloromethane, chloroform, hexane,heptane, cyclohexane, ethyl acetate, benzene, or toluene.

The materials of the invention, either particles or monoliths, may besurface modified by formation of an organic covalent chemical bondbetween an inorganic or organic group of the material and a surfacemodifier. The surface modifier may be an organic group surface modifier,a silanol group surface modifier, a polymeric coating surface modifier,or combinations thereof. For example, the surface modifier may have theformula Z_(a)(R′)_(b)Si—R, as described herein above. Also, the surfacemodifier may be a polymer coating, such as Sylgard®. Likewise, thesurface modifier may be octyltrichlorosilane, octadecyltrichlorosilane,octyldimethylchlorosilane, or octadecyldimethylchlorosilane.Additionally, the surface modifier is a combination of an organic groupsurface modifier and a silanol group surface modifier; a combination ofan organic group surface modifier and a polymeric coating surfacemodifier; a combination of a silanol group surface modifier and apolymeric coating surface modifier; or a combination of an organic groupsurface modifier, a silanol group surface modifier, and a polymericcoating surface modifier. The surface modifier may also be a silanolgroup surface modifier.

The invention also pertains to porous inorganic/organic homogenouscopolymeric hybrid monolith materials. In preferred embodiments, themonoliths comprise coalesced porous inorganic/organic homogenouscopolymeric hybrid particles having at least about 10% carbon content bymass, about 15% to about 90% carbon content by mass, about 25% to about75% carbon content by mass, about 30% to about 45% carbon content bymass, about 31 % to about 40% carbon content by mass, about 32% to about40% carbon content by mass, about 30% to about 45% carbon content bymass, about 15 to about 35% carbon content by mass, or about 15 to about20% carbon content by mass.

The inorganic portion of the hybrid monolith materials of the inventionmay be alumina, silica, titanium oxide, zirconium oxide, or ceramicmaterials.

For example, the invention relates to aporous inorganic/organichomogenous copolymeric hybrid material of the formula:

(A)_(x)(B)_(y)(C)_(z)  Formula I

wherein the order of repeat units A, B, and C may be random, block, or acombination of random and block; A is an organic repeat unit which iscovalently bonded to one or more repeat units A or B via an organicbond; B is an organosiloxane repeat unit which is bonded to one or morerepeat units B or C via an inorganic siloxane bond and which may befurther bonded to one or more repeat units A or B via an organic bond; Cis an inorganic repeat unit which is bonded to one or more repeat unitsB or C via an inorganic bond; and 0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210.The relative values of x, y, and z may also be 0.003≦y/z≦50 and0.02≦x/(y+z)≦21 or 0.03≦y/z≦5 and 0.2≦x/(y+z)≦2.1.

Similarly, the invention relates to a porous inorganic/organichomogenous copolymeric hybrid material of the formula:

(A)_(x)(B)_(y)(B*)_(y)*(C)_(z)  Formula II

wherein the order of repeat units A, B, B*, and C may be random, block,or a combination of random and block; A is an organic repeat unit whichis covalently bonded to one or more repeat units A or B via an organicbond; B is an organosiloxane repeat unit which is bonded to one or morerepeat units B or B* or C via an inorganic siloxane bond and which maybe further bonded to one or more repeat units A or B via an organicbond, B* is an organosiloxane repeat unit that does not have reactive(i.e., polymerizable) organic components and may further have aprotected functional group that may be deprotected after polymerization;C is an inorganic repeat unit which is bonded to one or more repeatunits B or B* or C via an inorganic bond; and 0.0003≦(y+y*)/z≦500 and0.002≦x/(y+y*+z)≦210.

Another aspect of the invention is a porous inorganic/organic homogenouscopolymeric hybrid material of the formula:

(A)_(x)(B)_(y)  Formula III

wherein the order of repeat units A and B may be random, block, or acombination of random and block; A is an organic repeat unit which iscovalently bonded to one or more repeat units A or B via an organic bond(e.g., a polymerized olefin); B is an organosiloxane repeat unit whichmay or may not be bonded to one or more repeat units B via an inorganicsiloxane bond and which may be further bonded to one or more repeatunits A or B via an organic bond; and 0.002≦x/y≦210.

Another aspect of the invention is a porous inorganic/organic homogenouscopolymeric hybrid material of the formula:

(A)_(x)(B)_(y)(B*)_(y)*  Formula IV

wherein the order of repeat units A, B, and B* may be random, block, ora combination of random and block; A is an organic repeat unit which iscovalently bonded to one or more repeat units A or B via an organic bond(e.g., a polymerized olefin); B is an organosiloxane repeat unit whichmay or may not be bonded to one or more repeat units B via an inorganicsiloxane bond and which may be further bonded to one or more repeatunits A or B via an organic bond; B* is an organosiloxane repeat unitthat does not have reactive (i.e., polymerizable) components and has aprotected functional group that may be deprotected after polymerization,but added as a third repeat unit. The relative stoichiometry of the A to(B+B*) components is the same as above, e.g., 0.002≦x/(y+y*)≦210.

Repeat unit A may be derived from a variety of organic monomer reagentspossessing one or more polymerizable moieties, capable of undergoingpolymerization, e.g., a free radical-mediated polymerization. A monomersmay be oligomerized or polymerized by a number of processes andmechanisms including, but not limited to, chain addition and stepcondensation processes, radical, anionic, cationic, ring-opening, grouptransfer, metathesis, and photochemical mechanisms.

A may also be one of the following:

wherein each R is independently H or a C₁-C₁₀ alkyl group (e.g, methyl,ethyl, or propyl); m is an integer of from 1 to about 20; n is aninteger of from 0 to 10; and Q is hydrogen, N(C₁₋₆alkyl)₃,N(C₁₋₆alkyl)₂(C₁₋₆alkylene-SO₃), or C(C₁₋₆hydroxyalkyl)₃.

Repeat unit B may be derived from several mixed organic-inorganicmonomer reagents possessing two or more different polymerizablemoieties, capable of undergoing polymerization, e.g., a freeradical-mediated (organic) and hydrolytic (inorganic) polymerization. Bmonomers may be oligomerized or polymerized by a number of processes andmechanisms including, but not limited to, chain addition and stepcondensation processes, radical, anionic, cationic, ring-opening, grouptransfer, metathesis, and photochemical mechanisms.

B may also be one of the following:

Repeat unit C may be —SiO₂— and may be derived from an alkoxysilane,such as tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS).

In one embodiment, A is a substituted ethylene group, B is aoxysilyl-substituted alkylene group, and C is a oxysilyl group, forexample the following:

In another example, the invention relates to a porous inorganic/organichomogenous copolymeric hybrid material of the invention may berepresented by the following formula:

wherein R₁ is H, F, Cl, Br, I, lower alkyl (e.g., CH₃ or CH₂CH₃); R₂ andR₃ are each independently H, F, Cl, Br, I, alkane, substituted alkane,alkene, substituted alkene, aryl, substituted aryl, cyano, ether,substituted ether, embedded polar group; R₄ and R₅ are eachindependently H, F, Cl, Br, I, alkane, substituted alkane, alkene,substituted alkene, aryl, substituted aryl, ether, substituted ether,cyano, amino, substituted amino, diol, nitro, sulfonic acid, cation oranion exchange groups, 0≦a≦2x, 0≦b≦4, and 0≦c≦4, provided that b+c≦4when a=1; 1≦d≦20, and 0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210.

The invention also relates to materials made by the novel methods of thepresent invention. For example, the invention pertains to a porousinorganic/organic homogenous copolymeric hybrid material prepared by thesteps of (a) copolymerizing an organic olefin monomer with analkenyl-functionalized organosiloxane, and (b) hydrolytic condensationof the product of step (a) with a tetraalkoxysilane. Likewise, theinvention pertains to a porous inorganic/organic copolymeric hybridmaterial prepared by the steps of (a) copolymerizing an organic olefinmonomer with an alkenyl-functionalized organosiloxane, and (b)hydrolytic condensation of the product of step (a) with atetraalkoxysilane, said material having at least 15% carbon content bymass.

The materials of the invention may be used as a liquid chromatographystationary phase; a sequestering reagent; a solid support forcombinatorial chemistry; a solid support for oligosaccharide,polypeptide, or oligonucleotide synthesis; a solid support for abiological assay; a capillary biological assay device for massspectrometry; a template for a controlled large pore polymer film; acapillary chromatography stationary phase; an electrokinetic pumppacking material; a polymer additive; a catalyst; or a packing materialfor a microchip separation device. The materials of the invention areparticularly suitable for use as a HPLC stationary phase or, in general,as a stationary phase in a separations device, such as chromatographiccolumns, thin layer plates, filtration membranes, sample cleanupdevices, and microtiter plates.

The porous inorganic/organic homogenous copolymeric hybrid particleshave a wide variety of end uses in the separation sciences, such aspacking materials for chromatographic columns (wherein such columns mayhave improved stability to alkaline mobile phases and reduced peaktailing for basic analytes), thin layer chromatographic (TLC) plates,filtration membranes, microtiter plates, scavenger resins, solid phaseorganic synthesis supports (e.g., in automated peptide oroligonucleotide synthesizers), and the like having a stationary phasewhich includes porous inorganic/organic homogenous copolymeric hybridparticles. The stationary phase may be introduced by packing, coating,impregnation, etc., depending on the requirements of the particulardevice. In a particularly advantageous embodiment, the chromatographicdevice is a packed chromatographic column, such as commonly used inHPLC.

EXAMPLES

The present invention may be further illustrated by the followingnon-limiting examples describing the preparation of porousinorganic/organic hybrid materials, and their use.

Example 1

One or more organoalkoxysilanes alone or in combination with a one ormore alkoxysilanes (all from Gelest Inc., Tullytown, Pa.) were mixedwith an alcohol (HPLC grade, J. T. Baker, Phillipsburgh, N.J.) and 0.1 Nhydrochloric acid (Aldrich Chemical, Milwaukee, Wis.) in a flask. Theresulting solution was agitated and refluxed for 16 hours in anatmosphere of argon or nitrogen. Alcohol was removed from the flask viadistillation at atmospheric pressure. Residual alcohol and volatilespecies were removed by heating at 115-140° C. for 1-2 hours in asweeping stream of argon or nitrogen or by heating at 125° C. underreduced pressure for 1-2 hours. The resulting polyorganoalkoxysiloxaneswere colorless viscous liquids. The chemical formulas are listed inTable 1 for the organotrialkoxysilanes and alkoxysilanes used to makethe product polyorganoalkoxysiloxanes (POS). Specific amounts are listedin Table 2 for the starting materials used to prepare these products.Example 1e was made from 298 g of (3-methacryloxypropyl)trimethoxysilaneand 221 g of octyltriethoxysilane. Example 1j was made frombis(trimethoxysilylpropyl)acrylamide and tetramethoxysilane. Thebis(trimethoxysilylpropyl)acrylamide was prepared separately from thereaction of 2 equivalents of bis(trimethoxysilylpropyl)amine (GelestInc., Tullytown, Pa.) and 1 equivalent of acryloyl chloride (AldrichChemical, Milwaukee, Wis.) in dry hexane (HPLC grade, J. T. Baker,Phillipsburgh, N.J.). The second equivalent of amine sequestered the HClcondensate of the amide formation, where the amine hydrochloride saltwas removed from the amide solution by filtration. The product structurewas confirmed by ¹H, ¹³C, and ²⁹Si NMR spectroscopy.

TABLE 1 Organoalkoxysilanes Alkoxysilane Alcohol Product ChemicalFormula Chemical Formula Chemical Formula 1a H₂C═C(CH₃)CO₂C₃H₆Si(OCH₃)₃na CH₃OH 1b H₂C═C(CH₃)CO₂C₃H₆Si(OCH₃)₃ Si(OCH₃)₄ CH₃OH 1c, dH₂C═C(CH₃)CO₂C₃H₆Si(OCH₃)₃ Si(OCH₂CH₃)₄ CH₃CH₂OH 1eH₂C═C(CH₃)CO₂C₃H₆Si(OCH₃)₃ na CH₃OH and C₈H₁₇Si(OCH₂CH₃)₃ 1f, gH₂C═CHC₆H₄(CH₂)₂Si(OCH₃)₃ Si(OCH₂CH₃)₄ CH₃CH₂OH 1h, i H₂C═CHSi(OCH₂CH₃)₃Si(OCH₂CH₃)₄ CH₃CH₂OH 1j H₂C═CHCON[C₃H₆Si(OCH₃)₃]₂ Si(OCH₂CH₃)₄ CH₃CH₂OH

TABLE 2 Organotrialkoxysilane Alkoxysilane 0.1N HCl Alcohol Product (g)(g) (g) (mL) 1a 497 na 54 300 1b 497 61 68 300 1c 170 1428 170 347 1d671 2250 304 788 1e 298 na 54 300 and 221 1f 15 355 42 99 1g 20 156 1947 1h 160 875 119 253 1i 799 1750 297 736 1j 27 395 47.3 229

Example 2

A solution of poly(vinyl alcohol) (PVA; 87%-89% hydrolyzed; Ave Mw13,000-23,000; Aldrich Chemical, Milwaukee, Wis.) in water was preparedby mixing and heating to 80° C. for 0.5 hours. Upon cooling, the PVAsolution was combined with a solution comprising divinylbenzene (DVB;80%; Dow Chemical, Midland, Mich.), a POS selected from Example 1,2,2′-azobisisobutyronitrile (AIBN; 98%, Aldrich Chemical), and or moreof the following coporogens: 2-ethylhexanoic acid (2-EHA; AldrichChemical), toluene (HPLC grade, J. T. Baker, Phillipsburgh, N.J.),cyclohexanol (CXL; Aldrich Chemical), 1-methyl-2-pyrrolidinone (NMP;Aldrich Chemical). The two solutions were mixed initially using amechanical stirrer with Teflon paddle and then emulsified by passing themixture through a static mixer for 10 minutes under an argon flow. Withcontinuous static mixing, the emulsification was heated to 70-80° C. ina period of 30 minutes. Thereafter, the emulsion was agitatedmechanically at 70-80° C. for 16 hours. Upon cooling, the suspension offormed particles was filtered and then washed consecutively with copiousamounts of water and then methanol. The particles were then dried at100° C. at a reduced pressure for 16 hours. Specific reagent amounts andreaction conditions are listed in Table 3. The specific surface areas(SSA), specific pore volumes (SPV) and the average pore diameters (APD)of these materials were measured using the multi-point N₂ sorptionmethod and are listed in Table 3 (Micromeritics ASAP 2400; MicromeriticsInstruments Inc., Norcross, Ga., or equivalent). The specific surfacearea was calculated using the BET method, the specific pore volume wasthe single point value determined for P/P₀>0.98, and the average porediameter was calculated from the desorption leg of the isotherm usingthe BJH method.

Example 3

A solution of Triton® X-45 (Aq X-45; Fluka, Milwaukee, Wis.), Triton®X-100 (Aq X-100; Fluka, Milwaukee, Wis.), or Methocel E15 (M E15, Dow,Grove City, Ohio; aqueous solution prepared by preheating water to 90°C. before addition of M E15 and cooling to 25° C.) in water and orethanol was prepared by mixing and heating to 60° C. for 0.5-1.0 hours.In a separate flask, a solution was prepared under a nitrogen purge atambient temperature by mixing for 0.5 hours divinylbenzene (DVB; 80%;Dow Chemical, Midland, Mich.; washed 3× in 0.1 N NaOH, 3× in water, andthen dried MgSO₄ from Aldrich Chemical), a POS selected from Example 1,2,2′-azobisisobutyronitrile (AIBN; 98%, Aldrich Chemical), and one ormore of the following reagents: toluene (HPLC grade, J. T. Baker,Phillipsburgh, N.J.), cyclohexanol (CXL; Aldrich, Milwaukee, Wis.),dibutylphthalate (DBP; Sigma; Milwaukee, Wis.), Triton® X-45 (Oil X-45;Fluka, Milwaukee, Wis.). For example 3f, 14 g of Pluronic® F-87 (F-87;BASF; Mount Olive, N.J.), was further added to the aqueous phase priorto mixing. For examples 3k, 3l, 3m, 3n, 3r, and 3v, 0.8 g (3k-3n) and4.5 g (3r, 3v) of tris(hydroxymethyl)aminomethane lauryl sulfate (TDS;Fluka, Milwaukee, Wis.) was further added to the aqueous solution priorto combination with the oil solution. For examples 3p and 3q, 2.8 and0.4 grams respectively of poly(vinyl alcohol) (PVA; 87%-89% hydrolyzed;Ave M_(w) 13,000-23,000; Aldrich Chemical) was further added to theaqueous solution prior to combination with the oil solution. The twosolutions were combined and then emulsified using a rotor/stator mixer(Model 100L, Charles Ross & Son Co., Hauppauge, N.Y.) for 4 minutesunder an argon flow. Next, a solution of 14.8 M ammonium hydroxide(NH₄OH; J. T. Baker, Phillipsburgh, N.J.) was added to the emulsion overa minute, and the emulsification was continued for 20 minutes. Forexample 3m and 3aa, the mixture was emulsified first, then heated at 80°C. for 1 hour prior to ammonium hydroxide addition. Thereafter, theemulsion was agitated mechanically at 80° C. for 16-24 hours. Uponcooling, the suspension of formed particles was filtered and then washedconsecutively with copious amounts of methanol, water and then methanol.The particles were then dried at 80° C. at a reduced pressure for 16hours. Specific reagent amounts and reaction conditions are listed inTable 4. The specific surface areas (SSA), specific pore volumes (SPV)and the average pore diameters (APD) of these materials are listed inTable 4 and were measured as described in Example 2. The % C values ofthese materials were measured by combustion analysis (CE-440 ElementalAnalyzer; Exeter Analytical Inc., North Chelmsford, Mass., orequivalent).

Example 4

A solution of Triton® X-45 (Aq X-45; Fluka, Milwaukee, Wis.) in waterand ethanol was prepared by mixing and heating to 60° C. for 0.5-1.0hours. In a separate flask, a solution was prepared under a nitrogenpurge at ambient temperature by mixing for 0.5 hours one or more organicmonomers selected from the following; divinylbenzene (DVB; 80%; DowChemical, Midland, Mich.; washed 3× in 0.1 N NaOH, 3× in water, and thendried MgSO₄ from Aldrich Chemical), Styrene (STY, 96%; Aldrich Chemical;washed 3× in 0.1 N NaOH, 3× in water, and then dried MgSO₄ from AldrichChemical), tert-butyl methacrylate (TBM, 98%, Aldrich Chemical),ethylene glycol dimethacrylate (EGD, 98%, Aldrich Chemical),1,4-Butanediol dimethacrylate (BDM, 95%, Aldrich Chemical),1-vinyl-2-pyrrolidinone (NVP, 99%, Aldrich Chemical), a POS selectedfrom Example 1, 2,2′-azobisisobutyronitrile (AIBN; 98%, AldrichChemical), cyclohexanol (CXL; Aldrich, Milwaukee, Wis.), and TritongX-45 (Oil X-45; Fluka, Milwaukee, Wis.). The two solutions were combinedand then emulsified using a rotor/stator mixer (Model 100L, Charles Ross& Son Co., Hauppauge, N.Y.) for 4 minutes under an argon flow. Next, asolution of 14.8 M ammonium hydroxide (NH₄OH; J. T. Baker,Phillipsburgh, N.J.) was added to the emulsion over a minute, and theemulsification was continued for 15 minutes. Thereafter, the emulsionwas agitated mechanically at 80° C. for 16-24 hours. Upon cooling, thesuspension of formed particles was filtered and then washedconsecutively with copious amounts of methanol, water and then methanol.The particles were then dried at 80° C. at a reduced pressure for 16hours. Specific reagent amounts and reaction conditions are listed inTable 5. The specific surface areas (SSA), specific pore volumes (SPV),the average pore diameters (APD) and the % C of these materials arelisted in Table 5 and were measured as described in Examples 2 and 3.

TABLE 3 POS POS DVB AIBN Toluene 2-EHA CXL NMP Water PVA SSA SPV APDProduct Reagent (g) (g) (g) (mL) (g) (g) (g) (mL) (g) % C (m²/g) (cm³/g)(Å) 2a 1a 102 174 1.8 242 0 0 0 1500 20 74.0 622 0.60 45 2b 1a 138 1381.8 242 0 0 0 1480 20 68.0 522 0.45 38 2c 1a 108 174 1.8 121 121 0 01500 20 — 506 0.57 50 2d 1a 75 75 1.1 0 182 0 0 1750 16 — 434 0.72 69 2e1a 55 96 1.1 0 182 0 0 1750 16 — 566 0.96 82 2f 1b 55 96 1.1 0 182 0 01750 16 72.3 585 1.12 95 2g 1b 55 96 1.1 0 132 0 0 1750 16 73.6 552 0.7971 2h 1b 55 96 1.1 80 52 0 0 1750 16 72.2 510 0.57 51 2i 1b 55 96 1.1 330 99 0 1750 16 — 545 0.41 37 2j 1b 55 96 1.2 83 0 0 83 1750 16 — 5120.34 32 2k 1b 60 90 1.2 33 0 0 132 1750 16 — 3 3 535

TABLE 4 Oil Aq POS Copor- Copor- Surfactant Surfac- Surfac- Prod- Re-POS DVB AIBN ogen ogen Type tant Ethanol Water tant SSA SPV APD uctagent (g) (mL) (g) Type (mL) Oil/Aq (g) (mL) (mL) (g) % C (m²/g) (cm³/g)(Å) 3a 1c 58 14 0.58 na na X-45/X-45 3.0 66 280 2.6 33.6 454 0.48 46 3b1c 58 14 0.10 toluene 7 X-45/X-45 3.5 66 280 2.5 31.3 479 0.59 50 3c 1c58 11 0.11 toluene 7 X-45/X-45 11.5 66 280 2.5 28.2 557 0.75 55 3d 1c 5814 0.15 CXL 20 X-45/X-45 3.5 66 280 2.5 32.3 557 0.85 64 3e 1c 58 140.19 CXL 20 X-45/X-45 11.5 66 280 2.5 33.3 630 1.11 72 3f 1c 58 14 1.78na na X-45/X-45 11.5 66 280 2.5 33.7 476 0.80 66 3g 1c 58 14 1.55 DBP 20X-45/X-45 11.5 66 280 2.5 31.2 608 1.09 74 3h 1c 58 14 1.35 CXL 27X-45/X-45 4.5 66 280 2.5 32.4 556 0.95 72 3i 1c 59 14 0.15 CXL 30X-45/X-45 11.5 66 280 2.5 32.3 572 1.21 84 3j 1c 58 14 0.15 CXL 40X-45/X-45 16.5 66 280 3.5 34.1 632 1.78 109 3k 1c 58 14 0.15 CXL 40X-45/X-45 16.5 66 280 2.5 31.8 628 1.00 62 3l 1c 58 14 0.15 CXL 40X-45/X-45 16.5 7 280 3.5 30.6 666 1.16 79 3m 1c 58 14 0.15 CXL 40X-45/X-45 16.5 7 280 3.5 31.3 634 1.6 100 3n 1c 59 14 0.15 CXL 40X-45/X-45 16.5 7 280 3.5 32.5 571 1.56 113 3o 1c 58 14 0.15 CXL 40X-45/X-45 20.0 0 280 0 31.7 566 1.39 96 3p 1c 58 14 0.15 CXL 40X-45/X-45 20.0 0 280 0 34.3 545 1.49 110 3q 1c 58 14 0.15 CXL 40X-45/X-45 20.0 0 280 0 31.4 568 1.45 104 3r 1c 500 112 1.30 CXL 344X-45/X-45 142 60 2400 30.2 31.5 573 1.67 117 3s 1c 58 14 0.15 CXL 40X-45/X-45 16.5 7 280 3.5 31.3 608 1.51 97 3t 1c 58 7 0.08 CXL 36X-45/X-45 14.5 7 280 3.5 24.5 592 1.86 123 3u 1c 45 25 0.25 CXL 40X-45/X-45 16.5 7 280 3.5 50.0 604 1.40 97 3v 1c 500 121 1.30 CXL 344X-45/X-45 142 60 2400 30.2 31.0 508 1.53 116 3w 1c 500 121 1.30 CXL 344X-45/X-45 142 60 2400 30.2 37.4 417 1.36 116 3x 1d 58 14 0.15 CXL 40X-45/X-45 3.5 7 280 3.5 40.7 760 1.08 54 3y 1c 58 14 0.15 toluene 26 —/X-100 0 66 280 14.0 37.5 514 1.09 83 3z 1c 58 14 0.15 CXL 14  —/X-1000 14 280 5.6 32.0 463 0.53 51 3aa 1c 58 14 0.20 CXL 18  —/M E15 0 0 2805.9 32.2 490 0.52 45 3ab 1j 50 5.0 0.02 toluene 6  —/X-100 0 57 241 4.816.9 455 0.81 71.6

TABLE 5 POS Copor- Copor- Oil Prod- Re- POS Organic Monomer AIBN ogenogen X-45 Ethanol Water Aq X-45 SSA SPV APD uct agent (g) Monomer (mL)(g) Type (mL) (g) (mL) (mL) (g) % C (m²/g) (cm³/g) (Å) 4a 1c 58 EGD 140.17 CXL 26 3.5 66 280 3.5 25.1 560 0.99 77 4b 1c 58 BDM 14 0.15 CXL 263.5 66 280 3.5 25.8 528 0.93 78 4c 1c 58 DVB/TBM 14/3 0.15 CXL 26 3.5 66280 3.5 33.9 559 0.97 76 4d 1c 58 DVB/NVP 12/3 0.15 CXL 26 3.5 66 2803.5 33.5 428 0.84 74 4e 1c 58 DVB/STY  7/7 0.15 CXL 26 3.5 66 280 3.526.9 544 0.90 70 4f 1c 58 DVB/STY  3/11 0.15 CXL 26 3.5 66 280 3.5 27.1514 0.91 72 4g 1c 58 STY 14 0.15 CXL 26 3.5 66 280 3.5 20.2 530 0.94 71

TABLE 6 POS POS DVB AIBN Coporogen Coporogen SSA SPV APD Product Reagent(g) (g) (g) Type (g) (m²/g) (cm³/g) (Å) 5a 1e 1.3 2.2 0.04 2-EHA 5.5 5170.82 88 5b 1e 1.3 2.2 0.04 DDL 5.9 452 0.71 100 5c 1e 1.3 2.2 0.04 CXL5.5 501 0.81 88 5d 1e 1.3 2.2 0.04 toluene/DDL 3.0/3.0 534 0.83 90

Example 5

Pyrex glass tubes (VWR, Bridgeport, N.J.) were derivatized using thefollowing procedure: Treat the glass surface to 2.5 molar sodiumhydroxide solution (Aldrich Chemical) for 16 hours at ambient roomtemperature, wash with copious amounts of water, treat the glass surfacewith concentrated hydrochloric acid (J. T. Baker) for 1 hour at ambientroom temperature, wash with copious amounts of water, and then dry at100° C. under reduced pressure. The glass surface was subsequentlyderivatized by treating for 16 hours at 50° C. with a mixture preparedfrom 19 g of pyridine (J. T. Baker), 12.5 g(3-methacryloxypropyl)trichlorosilane (Gelest Inc.), and 40 g of toluene(HPLC grade, J. T. Baker). The glass tubes were then washed withtetrahydrofuran (THF; J. T. Baker), water, and THF, and then dried at100° C. and reduced pressure.

To the derivatized tubes were added a solution comprising divinylbenzene(DVB; 80%; Dow Chemical), a POS selected from Example 1,2,2′-azobisisobutyronitrile (AIBN; 98%, Aldrich Chemical), and on ormore of the following coporogens: 2-ethylhexanoic acid (2-EHA; AldrichChemical), toluene (HPLC grade, J. T. Baker), cyclohexanol (CXL; AldrichChemical), 1-dodecanol (DDL; Aldrich Chemical). The filled tubes weresubsequently heated for 20 hours at 75° C. The resultant monolithicmaterials were washed by Soxhlet extraction using methanol (HPLC grade,J. T. Baker) for 16 hours and then dried at 80-100° C. and reducedpressure. The specific surface areas (SSA), specific pore volumes (SPV)and the average pore diameters (APD) of these materials are listed inTable 6 and were measured as described in Example 2.

Example 6

A solution of Triton® X-45 (Aq X-45; Fluka, Milwaukee, Wis.), Triton®X-100 (Aq X-100; Fluka, Milwaukee, Wis.), Triton® X-165 (Aq X-165;Sigma, St. Louis, Mo.), Triton® X-305 (Aq X-305; Sigma, St. Louis, Mo.),Triton® X-705 (Aq X-705; Sigma, St. Louis, Mo.), or ammoniumlaurylsulfate (Aq ALS, Fluka, Milwaukee, Wis., 30% solution by weight inwater) in water and or ethanol was prepared by mixing and heating to 60°C. for 0.5-1.0 hours. In a separate flask, a solution was prepared undera nitrogen purge at ambient temperature by mixing for 0.5 hoursdivinylbenzene (DVB; 80%; Dow Chemical, Midland, Mich.; washed 3× in 0.1N NaOH, 3× in water, and then dried MgSO₄ from Aldrich Chemical), a POSselected from Example 1, 2,2′-azobisisobutyronitrile (AIBN; 98%, AldrichChemical), and on or more of the following reagents: toluene (HPLCgrade, J. T. Baker, Phillipsburgh, N.J.), cyclohexanol (CXL; Aldrich,Milwaukee, Wis.), and Triton® X-45 (Oil X-45; Fluka, Milwaukee, Wis.).For example 6b, 6c, and 6k, 0.4-1.9 g of ammonium laurylsulfate (Aq ALS,Fluka, Milwaukee, Wis., 30% solution by weight in water) was furtheradded to the aqueous phase prior to combination with the oil solution.The two solutions were combined and then emulsified using a rotor/statormixer (Model 100L, Charles Ross & Son Co., Hauppauge, N.Y.) for 13-27minutes under an argon flow. Next, a solution of 14.8 M ammoniumhydroxide (NH₄OH; J. T. Baker, Phillipsburgh, N.J.) was added to theemulsion over a minute, and the emulsification was continued for 20minutes. Thereafter, the emulsion was agitated mechanically at 80° C.for 16-24 hours. Upon cooling, the suspension of formed particles wasfiltered and then washed consecutively with copious amounts of methanol,water and then methanol. The particles were then dried at 80° C. at areduced pressure for 16 hours. Specific reagent amounts and reactionconditions are listed in Table 7. The specific surface areas (SSA),specific pore volumes (SPV), the average pore diameters (APD) and the %C of these materials are listed in Table 7 and were measured asdescribed in Examples 2 and 3.

Example 7

Spherical, porous, hybrid inorganic/organic particles of Examples 3, 4,and 6 were mixed with either tris(hydroxymethyl)aminomethane (TRIS,Aldrich Chemical, Milwaukee, Wis.) or tetraethylammonium hydroxide (35weight % in water, TEAH, Aldrich Chemical, Milwaukee, Wis.) in asolution comprised of one or more of the following; water, ethanol (HPLCgrade, J. T. Baker, Phillipsburgh, N.J.), and pyridine (J. T. Baker,Phillipsburgh, N.J.), yielding a slurry. The resultant slurry was thenenclosed in a stainless steel autoclave and heated to between 140-165°C. for 20 hours. After the autoclave cooled to room temperature theproduct was filtered and washed repeatedly using water and methanol(HPLC grade, J. T. Baker, Phillipsburgh, N.J.), and then dried at 80° C.under vacuum for 16 hours. Specific hydrothermal conditions are listedin Table 8 (mL of base solution/gram of hybrid silica particle,concentration and pH of initial TRIS solution, reaction temperature).The specific surface areas (SSA), specific pore volumes (SPV), theaverage pore diameters (APD) and the % C of these materials are listedin Table 8 and were measured as described in Examples 2 and 3.

TABLE 7 POS Copor- Copor- Oil Aqueous Aq Prod- Re- POS DVB AIBN ogenogen X-45 Ethanol Water Surfactant Surfactant SSA SPV APD uct agent (g)(mL) (g) Type (mL) (g) (mL) (mL) Type (g) % C (m²/g) (cm³/g) (Å) 6a 1c58 14 0.15 toluene 10 0 66 300 X-45 4.9 32.6 475 0.57 48 6b 1c 58 110.11 toluene 7 11.5 66 280 X-45/ALS 2.5/1.9 28.4 557 0.74 55 6c 1c 58 110.11 toluene 7 11.5 66 280 X-45/ALS 2.5/0.4 29.3 567 0.81 57 6d 1c 58 140.15 toluene 10 0 14 300 X-100 7.0 31.2 491 0.57 51 6e 1c 58 14 0.15toluene 10 0 66 300 X-100 7.0 34.2 518 0.64 55 6f 1c 58 14 0.15 toluene10 0 66 300 X-165 7.0 32.3 463 0.65 62 6g 1c 58 14 0.15 toluene 10 0 0300 X-165 7.0 31.3 427 0.55 54 6h 1c 58 14 0.15 toluene 10 0 66 300X-165 1.0 31.6 392 0.49 48 6i 1c 58 14 0.15 toluene 10 0 66 300 X-1650.5 33.1 396 0.51 52 6j 1c 58 14 0.15 toluene 10 0 7 300 X-165 7.0 33.0446 0.56 53 6k 1c 58 14 0.15 toluene 10 0 7 300 X-165/ALS 7.0/1.1 33.0435 0.57 55 6l 1c 58 14 0.15 CXL 11 0 7 300 X-165 7.0 33.9 442 0.59 606m 1c 58 14 0.15 toluene 10 0 66 300 X-305 7.0 33.0 424 0.67 50 6n 1c 5814 0.15 toluene 10 0 0 300 X-305 7.0 31.7 379 0.52 50 6o 1c 58 14 0.15toluene 10 0 66 300 X-705 7.0 31.3 382 0.62 48 6p 1c 58 14 0.15 toluene10 0 132 300 X-705 7.0 31.9 396 0.80 59

TABLE 8 Ethanol Pyridine Amount Composition Composition Conc. Temp. SSASPV APD Loss in SSA Product Precursor (mL/g) (% Volume) (% Volume) Base(Molarity) pH (° C.) % C (m²/g) (cc/g) (Å) (m²/g) 7a 3i 5 0 10 TRIS 0.3010.4 160 32.0 547 1.28 98 25 7b 3h 10 0 30 TRIS 0.30 10.3 160 33.0 5480.99 80 8 7c 3h 10 0 10 TRIS 0.60 10.5 160 33.1 506 0.91 81 50 7d 3e 100 0 TEAH 0.10 12.7 165 35.0 469 1.09 97 161 7e 3e 10 20 0 TRIS 0.30 10.1155 32.3 570 1.12 82 60 7f 3e 10 20 0 TEAH 0.10 12.7 155 34.5 525 1.1290 105 7g 4e 10 0 0 TEAH 0.10 12.4 165 27.6 373 0.86 95 171 7h 4f 10 0 0TEAH 0.10 12.4 165 27.3 339 0.85 103 175 7i 3a 10 0 0 TEAH 0.10 12.7 16533.4 331 0.45 56 123 7j 3c 10 0 0 TEAH 0.10 12.7 165 28.6 397 0.76 81160 7k 6f 10 0 0 TEAH 0.10 12.8 165 33.6 345 0.62 83 118

Example 8

The particles of hybrid silica prepared according to Examples 3r, 3v,and 3w were blended and then separated by particle size into ˜3, ˜5, and˜7 μm fractions. A 5.0 g amount of 3 μm fraction was combined with 100mL of concentrated sulfuric acid (EM Science, Gibbstown, N.J.) andstirred at room temperature in a 1 L round-bottom flask. After stirringfor 1 hour, the solution was slowly added to a stirred solution of 400mL water, and the mixture was stirred for 10 minutes. The modifiedhybrid silica particles were filtered and washed successively withwater, methanol (J. T. Baker), and then dried at 80° C. under reducedpressure for 16 hours. The particles were analyzed as described inExamples 2 and 3 and shown to have the following properties: 30.3% C,607 m²/g specific surface area (SSA), 1.51 cc/g specific pore volume(SPV), and 113 Å average pore diameter (APD). The loading of sulfonicacid groups was determined to be 1.0 meq/gram as measured by titrationwith 0.1 N NaOH (Metrohm 716 DMS Titrino autotitrator with 6.0232.100 pHelectrode; Metrohm, Hersau, Switzerland, or equivalent).

Example 9

The particles of hybrid silica prepared according to Examples 3r, 3v,and 3w were blended and then separated by particle size into ˜3, ˜5, and˜7 μm fractions. The surface of a 3 μm material fraction was modifiedwith chlorodimethyloctadecylsilane (Aldrich Chemical, Milwaukee, Wis.)as follows: 5×10⁻⁶ moles of silane per square meter of particle surfacearea and 1.6 equivalents (per mole silane) of imidazole (AldrichChemical, Milwaukee, Wis.) were added to a mixture of 15 g of hybridsilica particle in 100 mL of toluene (J. T. Baker) and the resultantmixture was refluxed for 20 hours. The modified hybrid silica particleswere filtered and washed successively with water, toluene, 1:1 v/vacetone/water, and acetone (all solvents from J. T. Baker), and thendried at 80° C. under reduced pressure for 16 hours. The particles wereanalyzed as described in Examples 2 and 3 and shown to have thefollowing properties: 40.2% C, 333 m²/g specific surface area (SSA),1.13 cc/g specific pore volume (SPV), and 118 Å average pore diameter(APD). The surface concentration of octadecylsilyl groups was determinedto be 1.44 μmol/m² by the difference in particle % C before and afterthe surface modification as measured by elemental analysis.

Example 10

The particles of hybrid silica prepared according to Example 3b and 3vwere separated by particle size into ˜3 μm fractions. The 3 μm fractionswere tested for mechanical strength in the following manner: Thematerial of interest was slurry packed using a downward slurry techniquein a 3.9×10 mm cartridge at 500 psig to insure no crushing of particlesoccurs. The column packing apparatus comprised a high-pressure liquidpacking pump (Model No: 10-500FS100 SC Hydraulic Engineering Corp., LosAngeles, Calif., or equivalent). After packing, the cartridge was takenoff the packing chamber and any excess material was wiped off flush withthe cartridge face. The packed cartridge was then reattached to thechamber, which was filled with methanol. The cartridge was subjected toincreasing pack pressures where the time to displace 20 mL of methanolwas recorded at each 500 psig pressure increments from 500 psig to 9500psig. Approximately 30 to 40 seconds were allowed at each pressureincrement for the packed bed to stabilize at that pressure before thedisplacement time was measured. The time to displace 20 mL of methanolwas then converted into flow rate (mL/min) by dividing the 20 mLdisplaced by the time (in seconds) and multiplying the result by 60.

PACKING CONDITIONS Slurry Solvent: Methanol Restriction: 0.009″ × 60″Slurry/Chamber Vol.: 50 mL Valve Actuation: Closed Material Amount: 0.25g Pump Stroke Rate: 180/min. Pack Pressure: 500 psig Displacement:  55mL PACK PRESSURE at OPEN FLOW RATES 440 mls/min 9000 psig 360 mls/min6000 psig 240 mls/min 3000 psig

The principle of the test is as follows: The packed material in thesteel chromatographic cartridge (3.9×10 mm) is exposed to differentpressures (500-9000 psig) of a methanol effluent. At high pressures theparticle beds of weak materials can compact or crush, which results in arestriction of methanol flow. The closer the methanol flow remains tothe linear trend predicted for an ideal particle, the greater themechanical stability of the packed bed material. As a means to normalizedifferences in particle size and packing parameters, and make directcomparisons of the effect of pressure on the stability of the basematerials, the methanol flow rates are normalized to the flow obtainedfor the respective columns at 1000 psig back pressure.

A comparison of mechanical strength results is shown in FIG. 1 forcommercially available silica based (5 μm Symmetry® C₁₈, WatersCorporation) and polymeric based (7 μm Ultrastyragel™ 10⁶ Å and 7 μmUltrastyragel™ 10⁴ Å, Waters Corporation) materials and the two 3 μmfractions of Examples 3b and 3v. It is evident that the hybrid packingmaterial 3b is mechanically stronger than the polymeric based materialsand has comparable strength to the silica based material.

Example 11

A solution was prepared using 5 mL of an acetic acid solution (J. T.Baker, Phillipsburgh, N.J.), Pluronic F-38 (BASF Corporation, MountOlive, N.J.), 2,2′-azobisisobutyronitrile (AIBN; 98%, Aldrich Chemical,Milwaukee, Wis.) and a water soluble monomer, includingN-[tris(hydroxymethyl)methyl]acrylamide (THMMA, Aldrich Chemical,Milwaukee, Wis.), (3-acrylamidopropyl)trimethylammonium chloride (APTA,75 wt. % solution in water, Aldrich Chemical, Milwaukee, Wis.),[3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxideinner salt (MAPDAHI, Aldrich Chemical) or polyethylene glycoldimethacrylate (PEGDMA, Aldrich Chemical). This mixture was stirred for2 hours at room temperature, and then sonicated for 5 minutes. A 2 mLaliquot of a 4:1 v/v mixture of tetramethylorthosilicate (TMOS, AldrichChemical, Milwaukee, Wis.) and 3-(trimethoxysilyl)propylmethacrylate(MAPTMOS, Aldrich Chemical, Milwaukee, Wis.) was added to the solution,which was then stirred in an ice water bath for 1 hour, and for afurther 1 hour at room temperature. The solution was transferred to acylindrical glass container, and placed in a oven for 16-24 hours at 45°C. Following removal from the cylindrical container, the monoliths wererinsed with water and then left for 24 hours in a 0.1 N ammoniumhydroxide solution at 65° C. After this treatment, the monoliths werewashed with water, refluxed in methanol for 24 hours, and then dried for16-24 hours at 85° C. under reduced pressure. Specific reagent amountsand reaction conditions are listed in Table 9. The specific surfaceareas (SSA), specific pore volumes (SPV), the average pore diameters(APD) and the % C of these materials are listed in Table 9 and weremeasured as described in Examples 2 and 3.

TABLE 9 Monomer Amount F-38 AIBN AcOH SSA SPV APD Product Monomer (g)(g) (mg) (Molarity) % C (m²/g) (cm³/g) (Å) 11a PEGDMA- M_(n) ~875 0.49870.2001 5.7 0.02 29.5 380 0.38 40 11b PEGDMA- M_(n) ~875 0.7569 0.20016.5 0.02 23.2 260 0.33 47 11c PEGDMA- M_(n) ~875 0.7557 0.3980 5.8 0.1019.7 232 0.3 46 11d PEGDMA- M_(n) ~875 1.0099 0.3992 5.8 0.02 19.9 2050.38 57 11e PEGDMA- M_(n) ~875 0.5021 0.4019 5.1 0.01 16.3 494 0.7 6011f PEGDMA- M_(n) ~258 0.5052 0.2052 5.5 0.02 32.1 411 0.4 41 11gPEGDMA- M_(n) ~258 0.5091 0.1985 5.5 0.01 27.3 505 0.5 43 11h PEGDMA-M_(n) ~258 0.5132 0.4017 5.4 0.01 27.3 270 0.28 41 11i MAPDAHI 0.50030.2026 5.2 0.02 16.3 539 0.63 48 11j MAPDAHI 0.5021 0.4007 5.4 0.02 15.1542 0.66 49 11k MAPDAHI 0.5006 0.6000 5.9 0.02 15.4 536 1.25 109 11lAPTA 0.6661 0.4008 7.3 0.02 15.9 459 1.33 133 11m APTA 0.6533 0.4012 7.50.05 16.1 484 1.18 107 11n THMMA 0.5368 0.4062 5.6 0.01 14.9 575 0.66 4911o THMMA 0.5311 0.4019 5.2 0.05 17.3 583 0.53 38

Example 12

Monoliths synthesized in Example 11 were placed in a stainless steelautoclave and immersed in a solution of 0.3 Ntris(hydroxymethyl)aminomethane (TRIS, Aldrich Chemical, Milwaukee,Wis.). The solution was then heated to 155° C. for 22 hours. After theautoclave cooled to room temperature the products were washed repeatedlyusing water and methanol (HPLC grade, J. T. Baker, Phillipsburgh, N.J.),and then dried at 85° C. under reduced pressure. The specific surfaceareas (SSA), specific pore volumes (SPV), the average pore diameters(APD) and the % C of these materials are listed in Table 10 and weremeasured as described in Examples 2 and 3.

TABLE 10 SSA SPV APD Product Precursor % C (m²/g) (cm³/g) (Å) 12a 11a28.3 145 0.28 60 12b 11c 31.6 104 0.23 65 12c 11e 20.6 149 0.67 172 12d11f 29.9 75 0.13 47 12e 11g 27.3 76 0.21 70

Example 13

Monoliths made by the formulation of Examples 11e and 11h were immersedin glass vials containing a) dichloromethane, b) diethyl ether, c)toluene, d) methanol, e) water (pH 10—NaOH), f) water (pH 3—HCl), g)acetonitrile, h) dimethylsulfoxide, i) hexanes or j) tetrahydrofuran for24 hours. The diameter and length of each of the monoliths showed nodimensional changes in any of the solvents within experimental error asmeasured by electronic caliper (Model 62379-531, Control Company,Friendswood, Tex. or equivalent).

Example 14

A solution of poly(vinyl alcohol) (PVA; 87%-89% hydrolyzed; Ave M_(w)13,000-23,000; Aldrich Chemical, Milwaukee, Wis.) in 1000 mL water wasprepared by mixing and heating to 80° C. for 0.5 hours. Upon cooling,the PVA solution was combined with a solution comprising divinylbenzene(DVB; 80%; Dow Chemical, Midland, Mich.), N-vinyl pyrrolidinone (NVP,Aldrich Chemical, Milwaukee, Wis.), 3-(trimethoxysilyl)propylmethacrylate (MAPTMOS, Aldrich Chemical, Milwaukee, Wis.),2,2′-azobisisobutyronitrile (AIBN; 98%, Aldrich Chemical), and toluene(HPLC grade, J. T. Baker, Phillipsburgh, N.J.). The two solutions weremixed initially using a mechanical stirrer with Teflon paddle and thenemulsified by passing the mixture through a static mixer for 30 minutesunder an argon flow. The emulsion was heated to 70° C. with mechanicalagitation, and left to stir at this temperature for 16 hours. Uponcooling, the suspension of formed particles was filtered and then washedconsecutively with copious amounts of hot water (80-100° C.) and thenmethanol. The particles were then dried at 85° C. at a reduced pressurefor 16 hours. Specific reagent amounts and reaction conditions arelisted in Table 11. The specific surface areas (SSA), specific porevolumes (SPV), the average pore diameters (APD) and the % C of thesematerials are listed in Table 11 and were measured as described inExamples 2 and 3.

TABLE 11 DVB AIBN Toluene NVP MAPTMOS PVA SSA SPV APD Product (g) (g)(mL) (g) (g) (g) % C (m²/g) (cm³/g) (Å) 14a 175 1.9 243 77.3 39 20 79.8622 0.81 64 14b 174 1.9 243 103 77 20 77.3 394 0.32 35 14c 175 1.9 244103 39 20 80.0 642 0.81 60

Example 15

Spherical, porous, hybrid inorganic/organic particles of Example 14 weremixed in either 1.0 or 2.5 M solutions of NaOH in water (AldrichChemical, Milwaukee, Wis.), yielding a suspension. The resultantsuspension was then heated at 85-100° C. for 24-48 hours. After thereaction was cooled to room temperature the products were filtered andwashed repeatedly using water and methanol (HPLC grade, J. T. Baker,Phillipsburgh, N.J.), and then dried at 80° C. under vacuum for 16hours. This processing yielded free silanol groups, as evidenced by ²⁹SiCP-MAS NMR spectroscopy. Specific amounts and conditions are listed inTable 12 (mL base solution/gram hybrid particle, base concentration,reaction temperature, and reaction time). The specific surface areas(SSA), specific pore volumes (SPV), the average pore diameters (APD) andthe % C of these materials are listed in Table 12 and were measured asdescribed in Examples 2 and 3.

TABLE 12 Base Base Amount Conc. Time Temp. SSA SPV APD Product Precursor(mL/g) (Molarity) (h) (° C.) % C (m²/g) (cm³/g) (Å) 15a 14a 2.5 1.0 2485 79.8 675 0.86 65 15b 14b 2.5 1.0 24 85 76.6 536 0.40 35 15c 14c 2.51.0 24 85 79.0 700 0.90 63

Incorporation by Reference

The entire contents of all patents, published patent applications andother references cited herein are hereby expressly incorporated hereinin their entireties by reference.

Equivalents

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, numerous equivalents to thespecific procedures described herein. Such equivalents were consideredto be within the scope of this invention and are covered by thefollowing claims. The contents of all references, issued patents, andpublished patent applications cited throughout this application arehereby incorporated by reference.

1-55. (canceled)
 56. A porous inorganic/organic homogenous copolymerichybrid material of the formula:(A)_(x)(B)_(y)(C)_(z) wherein the order of repeat units A, B, and C maybe random, block, or a combination of random and block; A is an organicrepeat unit which is covalently bonded to one or more repeat units A orB via an organic bond; B is an organosiloxane repeat unit which isbonded to one or more repeat units B or C via an inorganic siloxane bondand which may be further bonded to one or more repeat units A or B viaan organic bond; C is an inorganic repeat unit which is bonded to one ormore repeat units B or C via an inorganic bond; and x, y are positivenumbers and z is a non negative number, wherein when z=0, then0.002≦x/y≦210, and when z≠0, then 0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210.57. A porous inorganic/organic homogenous copolymeric hybrid material ofthe formula:(A)_(x)(B)_(y)(B*)_(y)*(C)_(z) wherein the order of repeat units A, B,B*, and C may be random, block, or a combination of random and block; Ais an organic repeat unit which is covalently bonded to one or morerepeat units A or B via an organic bond; B is an organosiloxane repeatunits which is bonded to one or more repeat units B or B* or C via aninorganic siloxane bond and which may be further bonded to one or morerepeat units A or B via an organic bond; B* is an organosiloxane repeatunit which is bonded to one or more repeat units B or B* or C via aninorganic siloxane bond, wherein B* is an organosiloxane repeat unitthat does not have reactive (i.e., polymerizable) organic components andmay further have a protected functional group that may be deprotectedafter polymerization; C is an inorganic repeat unit which is bonded toone or more repeat units B or B* or C via an inorganic bond; and x, yare positive numbers and z is a non negative number, wherein when z=0,then 0.002≦x/(y+y*)≦210, and when z≠0, then 0.0003≦(y+y*)/z≦500 and0.002≦x/(y+y*+z)≦210. 58-65. (canceled)
 66. A porous inorganic/organichomogenous copolymeric hybrid material of the formula:

wherein R₁is H, F, Cl, Br, I, lower alkyl (e.g., CH₃ or CH₂CH₃); R₂ andR₃ are each independently H, F, Cl, Br, I, alkane, substituted alkane,alkene, substituted alkene, aryl, substituted aryl, cyano, ether,substituted ether, embedded polar group; R₄ and R₅ are eachindependently H, F, Cl, Br, I, alkane, substituted alkane, alkene,substituted alkene, aryl, substituted aryl, ether, substituted ether,cyano, amino, substituted amino, diol, nitro, sulfonic acid, cation oranion exchange groups, 0≦a≦2x, 0≦b≦4, provided that b+c≦4 when a=1;1≦d≦20, 0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210. 67-70. (canceled)
 71. Aseparations device comprising a material according to claim 56, 57 or66.
 72. The separations device according to claim 71, wherein saiddevice is selected from the group consisting of chromatographic columns,thin layer plates, filtration membranes, sample cleanup devices, andmicrotiter plates. 73-121. (canceled)
 122. The porous inorganic/organichomogenous copolymeric hybrid material of claim 56, wherein z=0 and thehybrid material is of the formula:(A)_(x)(B)_(y) wherein the order of repeat units A and B may be random,block, or a combination of random and block; A is an organic repeat unitwhich is covalently bonded to one or more repeat units A or B via anorganic bond; B is an organosiloxane repeat unit which may or may not bebonded to one or more repeat units B via an inorganic siloxane bond andwhich may be further bonded to one or more repeat units A or B via anorganic bond; and 0.002≦x/y≦210.
 123. The porous inorganic/organichomogenous copolymeric hybrid material of claim 57, wherein z=0 and thehybrid material is of the formula:(A)_(x)(B)_(y)(B*)_(y)* wherein the order of repeat units A, B, and B*may be random, block, or a combination of random and block; A is anorganic repeat unit which is covalently bonded to one or more repeatunits A or B via an organic bond; B is an organosiloxane repeat unitwhich may or may not be bonded to one or more repeat units B or B* viaan inorganic siloxane bond and which may be further bonded to one ormore repeat units A or B via an organic bond B* is an organosiloxanerepeat unit that does not have reactive (i.e., polymerizable) organiccomponents and may further have a protected functional group that may bedeprotected after polymerization; and 0.002≦x/(y+y*)≦210. 124-140.(canceled)